{"title":"N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization","authors":"Youfeng Han, Beibei Zhang, Zhixiang Wang, Xiangyu Chen","doi":"10.1016/j.gresc.2024.03.002","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.03.002","url":null,"abstract":"The photoredox radical-polar crossover paradigm is a valuable tool for 1,2-difunctionalization of alkenes. However, the use of unactivated alkyl halides as radical precursors remains far less developed. Here, we report a photoreductive -heterocyclic nitrenium-catalyzed radical-polar crossover for the 1,2-dicarbofunctionalization of alkenes by using unactivated alkyl and aryl iodides. These reactions can be carried out under simple, transition-metal-free conditions with easily obtainable materials such as alkyl/aryl halides, alkenes, and aldehydes. The reactions exhibit a broad range of substrate compatibility and good tolerance towards functional groups. This approach offers a new tool to unlock the compatibility of carbon skeletons.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"23 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140148085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Transaminase catalyzed asymmetric synthesis of active pharmaceutical ingredients","authors":"Yiman Cui, Yadong Gao, Licheng Yang","doi":"10.1016/j.gresc.2024.03.003","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.03.003","url":null,"abstract":"Chiral amine molecules constitute vital components of pharmaceutical ingredients. Recent years have witnessed a growing focus on the efficient synthesis of chiral amines. Transaminases, as catalysts, have emerged as green, efficient, and highly selective solutions for substrates containing ketones or aldehydes, demonstrating exceptional performance in the synthesis of active drug molecules and natural products. This review primarily centers on the application of transaminases in the synthesis of important drug molecules bearing chiral amine group on acyclic or cyclic backbones. We delve into specific examples, highlighting the catalytic prowess of the sole transaminase catalyst as well as the combination with other enzymes in cascade transformations. This review illustrates the primary challenges that transaminases face and provides practical solutions that have been developed in these contexts. These solutions encompass various strategies and techniques that enhance the applicability and efficiency of transaminase-catalyzed reactions. In closing, we offer an outlook on the future of transaminase applications, discussing potential developments and emerging areas where this green and selective catalysis may play a pivotal role.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"18 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140148130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aoxin Guo, Yuan Xu, Zhenhua Jia, Teck-Peng Loh, Xue-Wei Liu
{"title":"Unraveling chemical glycosylation: DFT insights into factors imparting stereoselectivity","authors":"Aoxin Guo, Yuan Xu, Zhenhua Jia, Teck-Peng Loh, Xue-Wei Liu","doi":"10.1016/j.gresc.2024.03.004","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.03.004","url":null,"abstract":"Stereoselective chemical glycosylation reactions are pivotal for preparing manifold biologically and medically important compounds, while mechanisms of chemical glycosylation reactions remain obscure and largely speculative. Herein, we performed DFT calculations to delve into the multifaceted mechanistic details of glycosylation reactions, including the equilibria among reactive glycosyl triflate intermediates in solution, the stereoselectivity imparting protecting groups, solvent effects, base, and the anomeric effect. Our results provided theoretical corroborations to 2-OAc neighbouring group participation (NGP), the arming/disarming effect, the coordination theory of solvent effect on glycosylation stereochemistry, and the influence of solvent polarity on the reaction kinetics spanning the S1-S2 continuum. For the first time, the existence of putative contact-ion-pairs (CIP) of glycosyl oxocarbenium and triflate anion in organic solutions was theoretically confirmed with the identification of multiple ground state structures employing an implicit Solvation Model based on Density (SMD). Kinetics of nucleophilic attack of model glucosyl triflates by simple alcohol acceptors ethanol (EtOH) and trifluoroethanol (TFE), complexed with 2,4,6-tri--butylpyrimidine (TTBP) were explored, revealing the essential role of the close accompanying base for rendering glycosidic bond formation thermodynamically favorable. Our work deepens the comprehension of the glycosylation mechanism, paving the way for the rational design and future advancement of efficient and environmentally friendly stereoselective glycosylation reactions.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"62 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140148065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shengjie Song, Wenjian Wang, Jun Sun, Can Luo, Chunlei Wu, Jianjun Li
{"title":"Photo- and electro-induced perfluoroalkylation/cyclization of o-hydroxyaryl enaminones: Synthesis of perfluoroalkyl chromones","authors":"Shengjie Song, Wenjian Wang, Jun Sun, Can Luo, Chunlei Wu, Jianjun Li","doi":"10.1016/j.gresc.2024.03.001","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.03.001","url":null,"abstract":"A practical, metal-, and additive-free strategy for photo- and electro-induced perfluoroalkylation/cyclization of -hydroxyaryl enaminones with sodium perfluoroalkanesulfinates under mild conditions has been developed. Various fluoroalkyl chromones were efficiently assembled in moderate to good yields. The scalability of this protocol and the assembling of diverse nitrogen-containing heterocycles from late-stage transformations of fluoroalkyl chromones greatly broaden the practical applications of this developed protocol.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140148179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qian Zhou, Lulin Qiao, An-An Zhang, Lu Li, Tuan-Jie Meng, Baomin Fan, Yuan-Yuan Gao, Lantao Liu
{"title":"Enantioselective synthesis of planar chiral ferrocenes via gold(I)-catalyzed hydroarylation of N-ferrocenyl propiolamides","authors":"Qian Zhou, Lulin Qiao, An-An Zhang, Lu Li, Tuan-Jie Meng, Baomin Fan, Yuan-Yuan Gao, Lantao Liu","doi":"10.1016/j.gresc.2024.02.007","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.02.007","url":null,"abstract":"Herein, we report an intramolecular cyclization of -ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation. By using this protocol, a variety of planar chiral ferrocenopyridin-2(1)-ones were obtained in good yields and excellent enantioselectivities (up to 96% ).","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"73 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140098312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wen-Chao Gao, Wei Li, Juan Zhang, Hong-Hong Chang, Rong Zhou
{"title":"Mild and green thioacylation with dithiocarboxylates via photoredox catalysis","authors":"Wen-Chao Gao, Wei Li, Juan Zhang, Hong-Hong Chang, Rong Zhou","doi":"10.1016/j.gresc.2024.02.008","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.02.008","url":null,"abstract":"","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"28 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140098150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Palladium-catalyzed halosulfonylation of alkynes with ionic liquid as the green solvent and halide sources","authors":"Yin-Long Lai, Li-Yun Wu, Xun Xiong, Yi-Wei Lan, Yin-Yun Lin, Rui-Min Zhong, Huanfeng Jiang, Jianxiao Li","doi":"10.1016/j.gresc.2024.02.003","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.02.003","url":null,"abstract":"The first palladium-catalyzed halosulfonylation of alkynes with arylsulfonic acid under aerobic conditions was accomplished. This catalytic protocol provides a straightforward and effective synthetic strategy for the assembly of structurally diverse -halovinyl sulfones architectures with high atom- and step-economy and exceptional functional group tolerance. Notably, ionic liquid plays a crucial role in this catalytic system, which not only acts as an environmentally friendly solvent, but also provides the halide source. In the presence of 1 mol % of IPr-Pd-Cin-Cl as the catalyst, a wide range of terminal alkynes and internal alkynes could be excellently tolerated. Particularly, the developed catalytic system could be recycled up to five times and reused without significant loss of catalytic activity.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139980047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Siyuan Zhao, Hong Du, Qi Fang, Yuying Li, Lei Wu, Xiumei Liu, Feng Wang
{"title":"1,5-Pentanediol production from 3,4-dihydro-2H-pyran and acetic acid via successive reactions of esterification and hydrogenation","authors":"Siyuan Zhao, Hong Du, Qi Fang, Yuying Li, Lei Wu, Xiumei Liu, Feng Wang","doi":"10.1016/j.gresc.2024.02.005","DOIUrl":"https://doi.org/10.1016/j.gresc.2024.02.005","url":null,"abstract":"1,5-Pentanediol as an important chemical intermediate is commonly used for the manufacture of polyesters and polyurethanes. A novel process was developed for the production of bio-based 1,5-pentanediol (1,5-PDO) from 3,4-dihydro-2H-pyran (DHP) and acetic acid (AA) in this work. The esterification of DHP and AA achieved a 59.8% DHP conversion and 91.2% tetrahydropyran-2-yl acetate selectivity (THPOAc) at 373 K for 1 h and DHP/AA molar ratio of 1 without catalyst. Then the 1,5-PDO with selectivity of 54.5% was obtained from THPOAc via hydrogenation over Cu/Zn/Al catalyst under the conditions of 453 K and 50 bar. The higher dispersion of Cu nanoparticles, the larger surface area of metallic Cu, the higher amount of Cu active sites and the lower acidity of Cu/Zn/Al catalyst were beneficial for the hydrogenation of THPOAc to 1,5-PDO.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"143 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139980030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}